WO2023145665A1 - Composition de résine biodégradable, article moulé et procédé de production de composition de résine biodégradable - Google Patents

Composition de résine biodégradable, article moulé et procédé de production de composition de résine biodégradable Download PDF

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Publication number
WO2023145665A1
WO2023145665A1 PCT/JP2023/001818 JP2023001818W WO2023145665A1 WO 2023145665 A1 WO2023145665 A1 WO 2023145665A1 JP 2023001818 W JP2023001818 W JP 2023001818W WO 2023145665 A1 WO2023145665 A1 WO 2023145665A1
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WO
WIPO (PCT)
Prior art keywords
biodegradable resin
resin composition
magnesium sulfate
basic magnesium
hydrolysis inhibitor
Prior art date
Application number
PCT/JP2023/001818
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English (en)
Japanese (ja)
Inventor
徹 稲垣
哲生 高山
Original Assignee
宇部マテリアルズ株式会社
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Application filed by 宇部マテリアルズ株式会社 filed Critical 宇部マテリアルズ株式会社
Publication of WO2023145665A1 publication Critical patent/WO2023145665A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a biodegradable resin composition, a molded article, and a method for producing a biodegradable resin composition.
  • JP 2007-99794 A Japanese Patent Application Laid-Open No. 2020-132830
  • the present situation is that a biodegradable resin composition that gives a molded article having excellent rigidity and high mechanical properties has not yet been obtained. Therefore, the present invention provides a biodegradable resin composition that yields a molded article having excellent rigidity and high mechanical properties, a molded article having excellent rigidity and high mechanical properties, and a method for producing a biodegradable resin composition. intended to provide
  • the biodegradable resin composition according to the present invention contains a biodegradable resin, basic magnesium sulfate, and a hydrolysis inhibitor.
  • the molded article according to the present invention is a molded article of the biodegradable resin composition described above.
  • a method for producing a biodegradable resin composition according to the present invention is a method for producing a biodegradable resin composition containing a biodegradable resin, basic magnesium sulfate, and a hydrolysis inhibitor, comprising the following ( It has the steps of either 1) or (2). (1) a simultaneous addition step of simultaneously adding a hydrolysis inhibitor to a biodegradable resin together with basic magnesium sulfate; (2) A sequential addition step of adding a hydrolysis inhibitor to a biodegradable resin and then adding basic magnesium sulfate
  • a biodegradable resin composition that yields a molded article having excellent rigidity and high mechanical properties, a molded article having excellent rigidity and high mechanical properties, and a biodegradable resin composition are produced. can provide a method.
  • the biodegradable resin is selected from the group consisting of aliphatic polyester biodegradable resins and aromatic-aliphatic polyester biodegradable resins.
  • the biodegradable resin preferably has a weight average molecular weight in the range of 10,000 to 3,000,000, more preferably 50,000 to 1,000. More preferably, it is in the range of 0,000.
  • the weight average molecular weight of the biodegradable resin can be determined, for example, by GPC (gel permeation chromatography).
  • aliphatic polyester-based biodegradable resins include polylactic acid and hydroxycarboxylic acid polymers.
  • Hydroxycarboxylic acids can be selected from L-lactic acid, D-lactic acid, and DL-lactic acid.
  • a copolymer of lactic acid and hydroxycarboxylic acid can also be used as the biodegradable resin in the present invention.
  • polycondensates of aliphatic dicarboxylic acids and glycols are also known as aliphatic polyester-based biodegradable resins.
  • aliphatic dicarboxylic acids include succinic acid and adipic acid, and aliphatic polyester-based biodegradable resins synthesized by polycondensation of these with glycol can be preferably used.
  • succinic acid-based biodegradable resins examples include polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and polybutylene succinate lactate (PBSL).
  • PBS polybutylene succinate
  • PBSA polybutylene succinate adipate
  • PBSL polybutylene succinate lactate
  • PBSLC polybutylene succinate hydrocaproate
  • PBSC polybutylene succinate carbonate
  • PBST polybutylene succinate terephthalate
  • PBS-co-DEGS polybutylene succinate diethylene glycol succinate
  • PBS-co-BDGA polybutylene succinate-butylene
  • PBSF polybutylene succinate-fluorate
  • Adipic acid-based biodegradable resins include polybutylene adipate (PBA), polybutylene adipate terephthalate (PBAT), and polyethylene adipate terephthalate (PEAT).
  • PBA polybutylene adipate
  • PBAT polybutylene adipate terephthalate
  • PEAT polyethylene adipate terephthalate
  • biodegradable resins may be used singly or in combination of two or more.
  • polylactic acid (PLA) is preferable as the biodegradable resin in the present invention because of its excellent alkali resistance.
  • Basic magnesium sulfate is represented by MgSO4.5Mg (OH) 2.3H2O . It can be obtained by hydrothermal synthesis.
  • the shape of the basic magnesium sulfate is not particularly limited, and any shape of basic magnesium sulfate such as fibrous or fan-like can be used.
  • the average fiber length is generally 2 to 100 ⁇ m, preferably 5 to 50 ⁇ m
  • the average fiber diameter is generally 0.1 to 2.0 ⁇ m, preferably 0.1 to 1 ⁇ m. .0 ⁇ m range.
  • Basic magnesium sulfate generally has an average aspect ratio (average fiber length/average fiber diameter) of 2 or more, preferably 3-1000, more preferably 3-100, and particularly preferably 5-50.
  • the average fiber length and average fiber diameter of basic magnesium sulfate can be calculated from the number average values of the fiber length and fiber diameter measured by image analysis from an enlarged image obtained by a scanning electron microscope (SEM).
  • the content of basic magnesium sulfate is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, when the total mass of the biodegradable resin and basic magnesium sulfate is 100. .
  • a soft to hard biodegradable resin composition can be obtained.
  • wollastonite is known as an inorganic filler that is blended into biodegradable resins to improve physical properties. Since wollastonite does not dissolve in seawater, it is released into the ocean as a decomposition residue of biodegradable resins. In this case, accumulation of the released wollastonite can lead to unexpected problems.
  • the hydrolysis inhibitor is a compound that inhibits hydrolysis of the biodegradable resin, and examples thereof include compounds reactive with active hydrogen in the biodegradable resin. By adding such a compound, the amount of active hydrogen in the biodegradable resin can be reduced, and active hydrogen can be prevented from catalytically hydrolyzing the polymer chains constituting the biodegradable resin.
  • Hydrolysis inhibitors include, for example, isocyanate-based compounds and maleic acid-based compounds.
  • isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2 ,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene Diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene di
  • maleic acid compounds examples include maleic acid (CAS110-16-7), sodium maleate (CAS371-47-1), and potassium maleate (CAS689-82-7).
  • the content of the hydrolysis inhibitor is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, when the total mass of the biodegradable resin and basic magnesium sulfate is 100. .
  • the biodegradable resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired.
  • the biodegradable resin composition of the present invention can be produced by mixing each component and then melt-kneading. For example, first, a biodegradable resin, fibrous basic magnesium sulfate, and a hydrolysis inhibitor are mixed. A tumbler, a blender, a Henschel mixer, or the like can be used for mixing.
  • the remaining ingredients can be added to the biodegradable resin in any order.
  • Adding the fibrous basic magnesium sulfate and the hydrolysis inhibitor at the same time is advantageous in terms of cost reduction due to process simplification.
  • the hydrolysis inhibitor is added to the biodegradable resin and then the fibrous basic magnesium sulfate is added, the remaining fiber length of the fibrous basic magnesium sulfate after kneading becomes longer, and a higher reinforcing effect is obtained. be done.
  • the resulting mixture is melt-kneaded at 180 to 220° C. using a twin-screw extruder kneader or the like to obtain the biodegradable resin composition of the present invention.
  • the method for producing a biodegradable resin composition of the present invention is a method comprising either step (1) or (2) below.
  • step (1) or (2) below (1) Simultaneous addition step of simultaneously adding a hydrolysis inhibitor to a biodegradable resin together with basic magnesium sulfate (2) Adding a hydrolysis inhibitor to a biodegradable resin and then adding basic magnesium sulfate Sequential addition process.
  • molded articles can be produced by molding the biodegradable resin composition of the present invention.
  • a roll molding machine calender molding machine, etc.
  • a vacuum molding machine an extrusion molding machine, an injection molding machine, a blow molding machine, a press molding machine, or the like can be used.
  • the biodegradable resin composition of the present invention contains basic magnesium sulfate and a hydrolysis inhibitor, it is possible to obtain a molded product with excellent rigidity and high mechanical properties. Since the biodegradable resin composition of the present invention can be adjusted in flexural modulus by adjusting the content of basic magnesium sulfate, molded articles for various uses can be obtained.
  • the molded product of the present invention can be suitably used in a wide range of applications such as packaging materials for packaging liquids, powders, and solids such as various foods, medicines, miscellaneous goods, agricultural materials, and construction materials.
  • Specific uses include, for example, injection molded products (e.g. fresh food trays, coffee capsules, fast food containers, outdoor leisure products, etc.), extrusion molded products (films, e.g. fishing lines, fishing nets, vegetation nets, water retention sheets etc.), hollow molded products (bottles, etc.), and the like.
  • information electronic materials such as toner binders and thermal transfer ink binders, automotive interior parts such as electrical product housings, instrument panels, seats, and pillars, automotive exterior structural materials such as bumpers, front grills, and wheel covers. It can also be used for parts and the like.
  • packaging materials such as packaging films, bags, trays, capsules, bottles, cushioning foams, fish boxes and the like, and agricultural materials and the like.
  • Agricultural materials include, for example, mulching films, tunnel films, house films, shades, weed control sheets, ridge sheets, germination sheets, vegetation mats, nursery beds, flower pots and the like.
  • ⁇ Basic magnesium sulfate> A Fibrous basic magnesium sulfate MOS-HIGE A-1, manufactured by Ube Material Industries, Ltd., average major axis 15 ⁇ m, average minor axis 0.5 ⁇ m
  • B Polylactic acid Terramac TE-2000, manufactured by Unitika
  • C methylene diphenyl 4,4'-diisocyanate Reagent
  • A basic magnesium sulfate
  • B polylactic acid
  • C methylenediphenyl 4,4′-diisocyanate
  • Example 2 In the same manner as in Example 1, except that 15 parts by mass of basic magnesium sulfate (A), 85 parts by mass of polylactic acid (B), and 3 parts by mass of methylenediphenyl 4,4'-diisocyanate (C) were used. No. 2 resin composition was obtained.
  • Table 1 summarizes the formulations of the resin compositions of Examples and Comparative Examples.
  • ⁇ Flexural modulus> A three-point bending test was performed in accordance with JISK7171 using a universal testing machine (manufactured by Imada Co., Ltd.). The distance between fulcrums was 40 mm, and the load speed was 10 mm/min. The flexural modulus was evaluated from the load deflection curve obtained.
  • the weight average molecular weight of the resin composition after melt-kneading corresponds to the weight average molecular weight of polylactic acid.
  • Polylactic acid and the weight average molecular weight of the resin composition were calculated as polystyrene equivalent molecular weights by gel permeation chromatography (GPC) using HLC-8320GPC (manufactured by Tosoh Corporation). KG, K-805L and K-800d (manufactured by Shodex) were used as columns, and chloroform was used as an eluent.
  • Table 2 shows the flexural modulus of the molded body produced using each resin composition together with the weight average molecular weight.
  • the weight average molecular weight of Comparative Example 1 represents the molecular weight of the polylactic acid itself used as the starting material.
  • Comparative Example 1 is polylactic acid alone, and neither basic magnesium sulfate nor a hydrolysis inhibitor is blended, so the flexural modulus of the obtained molded article cannot be increased. Since the resin compositions of Examples 1 and 2 contain a hydrolysis inhibitor together with basic magnesium sulfate, hydrolysis of polylactic acid by basic magnesium sulfate is suppressed. Therefore, in Examples 1 and 2, the weight average molecular weight of the same level as the raw material (Comparative Example 1) can be maintained. Moreover, by using the resin compositions of these examples, it is possible to obtain a molded article having an improved flexural modulus.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition de résine biodégradable selon la présente invention contient une résine biodégradable, du sulfate de magnésium basique et un inhibiteur d'hydrolyse.
PCT/JP2023/001818 2022-01-25 2023-01-23 Composition de résine biodégradable, article moulé et procédé de production de composition de résine biodégradable WO2023145665A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-009343 2022-01-25
JP2022009343 2022-01-25

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WO2023145665A1 true WO2023145665A1 (fr) 2023-08-03

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008101084A (ja) * 2006-10-18 2008-05-01 Unitika Ltd 難燃かつ耐衝撃性ポリ乳酸樹脂組成物およびそれを成形してなる成形体
JP2010270309A (ja) * 2009-04-24 2010-12-02 Sumitomo Chemical Co Ltd 樹脂組成物の製造方法及び成形体
WO2015159832A1 (fr) * 2014-04-16 2015-10-22 帝人株式会社 Transducteur qui utilise des fibres et qui utilise un signal électrique comme entrée ou sortie
CN112920577A (zh) * 2021-02-02 2021-06-08 苏州塑发生物材料有限公司 高表面质量镁盐晶须纤维增强聚乳酸复合材料及其制备方法
WO2021199840A1 (fr) * 2020-03-30 2021-10-07 宇部マテリアルズ株式会社 Accélérateur de dégradation pour résine biodégradable à base de polyester aliphatique, composition de résine biodégradable, et procédé d'accélération de dégradation de résine biodégradable à base de polyester aliphatique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008101084A (ja) * 2006-10-18 2008-05-01 Unitika Ltd 難燃かつ耐衝撃性ポリ乳酸樹脂組成物およびそれを成形してなる成形体
JP2010270309A (ja) * 2009-04-24 2010-12-02 Sumitomo Chemical Co Ltd 樹脂組成物の製造方法及び成形体
WO2015159832A1 (fr) * 2014-04-16 2015-10-22 帝人株式会社 Transducteur qui utilise des fibres et qui utilise un signal électrique comme entrée ou sortie
WO2021199840A1 (fr) * 2020-03-30 2021-10-07 宇部マテリアルズ株式会社 Accélérateur de dégradation pour résine biodégradable à base de polyester aliphatique, composition de résine biodégradable, et procédé d'accélération de dégradation de résine biodégradable à base de polyester aliphatique
CN112920577A (zh) * 2021-02-02 2021-06-08 苏州塑发生物材料有限公司 高表面质量镁盐晶须纤维增强聚乳酸复合材料及其制备方法

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